Bromine → HCID 13752482, compound

HRID 256112Notes

Reaction equation

HRID 256112 reaction equation
[Br:1]Br.[S:3]1[C:11]2[C:6](=[N:7][C:8]([C:16]([O:18][CH3:19])=[O:17])=[C:9]([C:12]([O:14][CH3:15])=[O:13])[CH:10]=2)[CH:5]=[CH:4]1.C([O-])(=O)C.[Na+].S(=O)(O)[O-].[Na+]>C(O)(=O)C.C(OCC)(=O)C>[Br:1][C:5]1[C:6]2=[N:7][C:8]([C:16]([O:18][CH3:19])=[O:17])=[C:9]([C:12]([O:14][CH3:15])=[O:13])[CH:10]=[C:11]2[S:3][CH:4]=1

Participants

7

Reactant 4

HCID 24408Bromine3×HCID 517045Sodium Acetate2×HCID 13729656HCID 13729656, compoundHCID 23665763Sodium Bisulfite

Product 1

HCID 13752482HCID 13752482, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent3×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
85 °C

Procedure

A solution of bromine (20 g, 0.125 mol) in acetic acid (50 mL) is added dropwise over three hours to a solution of dimethyl thieno[3,2-b]pyridine-5,6-dicarboxylate, (26.3 g, 0.104 mol), containing sodium acetate (17.2 g, 0.2 mol) in acetic acid (300 mL) at 85° C. Additional sodium acetate (18 g) and bromine (20 g) in acetic acid (50 mL) is added over an hour and the mixture stirred at 85° C. overnight. Bromine (10 g) is added in one portion then left at 85° C. for four hours. The mixture is cooled and treated with aqueous sodium bisulfite, diluted with ethyl acetate and concentrated. The reaction product is partitioned between water and methylene chloride and the organic layer washed with aqueous sodium chloride and the solvent removed. The residue is washed with ether to give 25 g of crude product, mp 165°-168° C. Recrystallization from methanol gave needles of dimethyl 3-bromothieno[ 3,2-b]pyridine-5,6-dicarboxylate, mp 168°-169° C.

Workup

  1. waitthen left at 85° C. for four hours
  2. temperatureThe mixture is cooled
  3. concentrationconcentrated
  4. customThe reaction product is partitioned between water and methylene chloride
  5. washthe organic layer washed with aqueous sodium chloride
  6. customthe solvent removed
  7. washThe residue is washed with ether
  8. customto give 25 g of crude product, mp 165°-168° C
  9. customRecrystallization from methanol

Sources & evidence

ORD record
ord-625df7e41f344d05bb47b784d77dbb6e
Source dataset
uspto-grants-1987_10
Patent number
US04701208

Reaction notes

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